This thesis is part of a joint thermochemical heat storage (TCS) research project named Neutrons for Heat Storage (NHS), involving three Nordic research institutes. The project isfunded by Nordforsk and KTH Royal Institute of Technology for the project partner KTH. KTH´s objective in the NHS project is to design, build and operate a bench-scale TCS system using strontium chloride (SrCl2) and ammonia (NH3) as a solid-gas reaction system for low temperature heat storage (40-100 ℃). Here, absorption of NH3 into SrCl2⋅NH3 (monoammine) to form SrCl2⋅8NH3 (octaammine) is used for heat release, and desorption (of NH3 from SrCl2⋅8NH3 to form SrCl2⋅NH3) for heat storage. This thesis initially aimed to conduct commissioning, operation and experimental data acquisition, and performance evaluation of the bench-scale TCS system. However, due to various delays in equipment delivery and shortcomings discovered during the project timeline, its objectives were then redefined to partially commission the system with NH3 and carry out the first absorption cycle in one of the reactors. This thesis project was partly a joint project, where Hjörtur Brynjarsson performed various tasks in the overarching NHS project as part of his thesis project, alongside the work described in this report. Brynjarsson’s work involved reviewing and adapting the design of this bench-scale TCS system. For further details about the shortcomings discovered and corresponding design adaptations, readers are referred to Brynjarsson’s report. In this thesis project, to understand the design of the TCS system, background research on the current project and the SrCl2-NH3 reaction pair was conducted. This includes comprehending the evolution of the project carried out by the previous students and project researchers to the current thesis project. Following this, the maximum theoretical volume of composites in the reactor-heat exchanger (R-HEX) was determined. This was found to be 5262 cm3, and the corresponding SrCl2 in the R-HEX is 1631 g for an average salt density in the composite of 0.31g/cm3. Thereupon, a literature review was conducted on the performance evaluation of Thermal energy storage (TES) systems. The final report of International Energy Agency (IEA) Annex 30 (on Applications of TES in the Energy Transition: Benchmarks and Developments) presents numerous Key Performance Indicators (KPIs) relevant to TES systems and are classified into technical, economic, and lifetime performance indicators. These KPIs are used as the basis for the current thesis work and are compared to examples from other metalhalide-NH3 TCS systems. Finally, for the current thesis project, it was decided to focus the KPIs on technical performance indicators, such as energy storage capacity [kJ] and reaction advancement [-]. As one of the main tasks within the project, the data acquisition system (for measuring temperature, pressure, and mass flow rate parameters), as well as the system components and many final connections, were commissioned herein. A data acquisition manual is thus provided for future use. It considers all the data measuring instruments and their respective locations in the system and the data logger. Also, explanations are provided for the calibration of these instruments. As the next main task, a thermal homogeneity test of the reactors (to compare the heat transfer similarity of reactors before the first reaction) was performed, to investigate the underlying assumption that the reactors were identical was valid. After conducting the test, it was found that reactor A had slightly better heat transfer than reactor B. However, this inhomogeneity is not significant enough to affect the system’s overall performance. As the final main task, partial commissioning of the system (i.e., for the first absorption reaction in reactor B) with N2 (as a mock-test to troubleshoot the procedure forNH3) and then with NH3 were carried out. During the partial commissioning of the system using NH3, the NH3 was added in short pressure pulses (between 5-8 bar(a)) with idling between each pulse due to some practical reasons. In addition to this, the absorption reaction was carried out under less than ideal (still not unfavourable) absorption conditions by deliberately setting the heat transfer fluid (HTF) at high temperatures (e.g., at 105, 90, and 65 °C) to avoid a drastic pressure drop in the reactor between each NH3 pulse. At the end of the NH3 commissioning (possible completion of absorption), it was found that 1541 g of NH3 passed through the mass flow meter. The most likely scenario is that 1521 g of NH3 reacted with the SrCl2 salt in the reactor (the rest, 20 g, is in the dead space, comprised of, e.g., the voids in composite, voids in the R-HEX, and the volume in the gas lines). The heat released from the absorption reaction, in this case, is 3774 kJ (or 1.05 kWh), considering all eight ammines. The heat released from the absorption reaction of SrCl2∙NH3 (monoammine) to SrCl2∙8NH3 (octaammine) is 3224 kJ (or 0.89 kWh). The discharge power calculation is excluded here due to the special approach used in this first absorption, with long idling steps, making that irrelevant. In addition, the sustainability aspects of this TCS technology (SrCl2-NH3) used in this project were analyzed. Based on the analysis, it was found that this technology is environmentally friendly, economically feasible, and can aid in social development. Hence, this technology is considered sustainable, and the designed TCS system has an overall positive impact on sustainable development. To conclude, within this project, the designed TCS system was successfully operated for the first absorption in one reactor and is found to meet the design storage capacity (0.89 kWh). As this TCS system was mainly operated for data acquisition, and since the first absorption was performed at less-than ideal conditions, better absorption conditions are recommended for the subsequent cycles, accommodating better temperature and pressure conditions for both absorption and desorption reactions. Finally, evaluation of the system's technical performance at different reaction conditions (pressure, temperature) and optimizing the system for energy and economics are some of the key follow-up tasks for future work that will benefit the system. / Detta exjobbsprojekt är en del av ett forskningsprojekt Neutrons for Heat Storage (NHS), som handlar om termokemisk energilagring (TCS) och genomfördes med hjälp av tre nordiska forskningsinstitut. Projektet finansieras av Nordforsk och KTH Kungliga Tekniska Högskolan för KTH. I NHS-projektet, KTH:s mål är att utforma, bygga och driva ett TCS-system i bänkskala med ett fast-gasreaktionssystem som använder reaktionsparet strontiumklorid (SrCl2) och ammoniak (NH3), för värmelagring vid låg temperatur (t.ex. 40-100 ℃). Här används specifikt absorption av NH3 i SrCl2⋅NH3 (monoammin) till SrCl2⋅8NH3 (oktaammin) för värmeavgivning och desorption av NH3 från SrCl2⋅8NH3 till SrCl2⋅NH3 för värmelagring. Detta projekt syftade inledningsvis till att genomföra driftsättning, drift och insamling av experimentella data samt utvärdering av prestanda för TCS-systemet i bänkskala. På grund av olika förseningar i leveransen av flertal utrustningar och brister som upptäcktes under projektets gång, omdefinierades målen till att ta en partiell driftsättning av systemet med NH3 och genomföra den första absorptionscykeln i en av reaktorerna. Detta exjobbsprojekt var delvis ett gemensamt projekt, där Hjörtur Brynjarsson utförde olika uppgifter i det övergripande NHS-projektet som en del av sitt exjobbsprojekt, parallelt med arbetet som beskrivs i denna rapport. Brynjarsson’s arbete bestod i att granska och anpassa utformningen av denna bänkskala i TCS-system. För ytterligare detaljer om de brister som upptäcktes och motsvarande anpassningar av utformningen hänvisas läsarna till Brynjarsson’s rapport. I detta exjobbsprojekt, för att förstå TCS-systemets utformning, genomfördes bakgrundsforskning om det aktuella NHS projektet och reaktionsparet SrCl2-NH3. Detta innefattar att förstå utvecklingen av NHS projektet från tidigare projekt utförda av studenter och projektforskare för att sammanställa detta exjobbsprojekt. Därefter fastställdes i detta projekt den maximala teoretiska volymen kompositer i reaktor-värmeväxlare enheten (RHEX). Den visade sig vara 5262 cm3 och att motsvarande SrCl2 i R-HEX är 1631 g för en genomsnittlig salttäthet i kompositen på 0,31 g/cm3. Därefter gjordes en litteraturstudie om utvärdering av prestanda för system för termisk energilagring (TES). Slutrapporten om bilaga 30 från International Energy Agency (IEA) (om tillämpningar av TES i energiomställningen: Benchmarks och Utvecklingar) presenterar ett flertal nyckelindikatorer (KPI:er) för prestandaanalys som är relevanta för TES-system och som är klassificerade i tekniska, ekonomiska och livslängdsindikatorer. Dessa KPI:er används som grund för den aktuella exjobben och jämförs med exempel från andra metallhalogenid-NH3- TCS-system. För detta exjobbprojektet beslutades slutligen att fokusera KPI:erna på tekniska prestandaindikatorer, t.ex. energilagringskapacitet [kJ] och reaktionsframsteg [-]. Som en av huvuduppgifterna inom detta projekt togs datainsamlingssystemet (för mätning av temperatur, tryck och massflödesparametrar) samt systemkomponenterna och många slutliga anslutningar i drift här. En användarmanual för datainsamling tillhandahålls därför för framtida användning. Den gäller alla instrument för datamätning och deras respektive placering i systemet samt dataloggern. Dessutom ges här förklaringar till kalibreringen av dessa instrument. Som nästa huvuduppgift utfördes ett test av reaktorernas termiska homogenitet (för att jämföra reaktorernas likhet i värmeöverföring före den första reaktionen), för att undersöka om det underliggande antagandet att reaktorerna var identiska var giltigt. Efter att ha utfört testet konstaterades det att reaktor A hade en något bättre värmeöverföring än reaktor B. Denna inhomogenitet är dock inte tillräckligt betydande för att påverka systemets totala prestanda. Som sista huvuduppgift genomfördes en partielldriftsättning av systemet (dvs. för den första absorptionsreaktionen i reaktor B) med N2 (som ett simuleringstest för att felsöka förfarandet för NH3) och sedan med NH3. Under den partiella idrifttagningen av systemet med NH3 tillsattes NH3 i korta tryckpulser (mellan 5-8 bar(a)) med tomgång mellan varje puls av praktiska skäl. Dessutom utfördes absorptionsreaktionen under mindre än ideala (men ändå inte ogynnsamma) absorptionsförhållanden genom att värmeöverföringsvätskan medvetet ställdes in på höga temperaturer (t.ex. 105, 90 och 65 °C) för att undvika en drastisk tryckminskning i reaktorn mellan varje NH3-puls. I slutet av NH3-installationen (eventuellt avslutad absorption) konstaterades att 1541 g NH3 passerade genom massflödesmätaren. Det mest sannolika scenariot är att 1521 g NH3 reagerade med SrCl2-saltet i reaktorn (resten dvs., 20 g, finns i det döda utrymmet, som t.ex.består av hålrummen i kompositen, hålrummen i R-HEX och volymen i gasledningarna). Den värme som frigörs från absorptionsreaktionen är i detta fall 3774 kJ (eller 1,05 kWh), om man beaktar alla åtta aminer. Den värme som frigörs från absorptionsreaktionen av SrCl2∙NH3 (monoammin) till SrCl2∙8NH3 (oktaammin) är 3224 kJ (eller 0,89 kWh). Beräkningen av utmatningseffekten är utesluten här på grund av det speciella tillvägagångssätt som används vid denna första absorption, med långa tomgångssteg, vilket gör att den är irrelevant. Dessutom analyserades hållbarhetsaspekterna av denna TCS-teknik (SrCl2-NH3) som användes i detta projekt. På grundval av analysen konstaterades det att denna teknik är miljövänlig, ekonomiskt genomförbar och kan bidra till social utveckling. Tekniken anses därför vara hållbar och det konstruerade TCS-systemet har en övergripande positiv inverkan på hållbar utveckling. Sammanfattningsvis kan man konstatera att det konstruerade TCS-systemet inom ramen för detta projekt används på ett framgångsrikt sätt för den första absorptionen i en reaktor och att det uppfyller den avsedda lagringskapaciteten (0,89 kWh). Eftersom detta TCS-system huvudsakligen användes för datainsamling och eftersom den första absorptionen utfördes under mindre än ideala förhållanden, rekommenderas bättre absorptionsförhållanden för de efterföljande cyklerna, med bättre temperatur- och tryckförhållanden för både absorptions och desorptionsreaktioner. Slutligen är utvärdering av systemets tekniska prestanda vid olika reaktionsförhållanden (tryck, temperatur) och optimering av systemet med avseende på energi och ekonomi några av de viktigaste uppföljningsuppgifterna för framtida arbete som kommer att gynna systemet.

Thermochemical heat storage (TCS) is a thermal energy storage (TES) technology used to store thermal energy for later use. TCS can provide heating or cooling services from intermittently available thermal energy, often low grade waste heat. The system studied here stores and releases the energy in the form of chemical energy by utilizing reversible chemical reactions. TCS has potential to reduce greenhouse gas emissions, increase infrastructure system efficiency, lower society-wide energy system costs and by that contribute to sustainable development. This thesis is part of a joint TCS research project named Neutrons for Heat Storage (NHS), involving three research institutes. The project is funded by Nordforsk and KTH Royal Institute of Technology. KTH´s objective in the NHS project is to design, build and operate a bench-scale TCS system using strontium chloride (SrCl2) and ammonia (NH3) as a solid-gas reaction system for low-temperature heat storage (40-80 ℃). Here, absorption of NH3 into SrCl2⋅NH3 (monoammine) to form SrCl2⋅8NH3 (octaammine) is used for heat release, and desorption (of NH3 from SrCl2⋅8NH3 to form SrCl2⋅NH3) for heat storage. Prior to this thesis project, this TCS system, as well as its reactor+heat exchanger (R-HEX) units, were numerically designed at KTH, and the R-HEX units were manufactured. This system is now being built at the laboratory of Applied Thermodynamics and Refrigeration division at the Department of Energy Technology, KTH. The initial system is comprised of a shared storage tank, expansion valve, ammonia meter and an R-HEX (absorption path); and an R-HEX, ammonia meter, gas cooler, compressor, condenser, and the storage tank (desorption path), to accommodate absorption, desorption, and NH3 storage. This thesis was originally planned to include commissioning, operation and experimental data acquisition, and performance evaluation of this system. However, due to various delays and shortcomings discovered at the beginning of the project, its objectives were then redefined to review the system and its components and propose necessary design adaptations of the initially designed (and partially built) system. This thesis project was partly a joint project, where Harish Seetharaman performed various tasks in the overarching NHS project as part of his own thesis project, performed alongside the work described in this report. For various information and results, referring to Harish´s report therefore will be necessary. A literature review of the research into SrCl2-NH3 systems was conducted, with emphasis on performance evaluation, kinetics, and reaction paths. TES performance evaluation is discussed concerning the TCS key performance indicators, with the 2018 IEA's Annex 30 as a guideline and 2013 IRENA´s E17 technology brief as a comparative reference. Much progress and refinement has been made in the 5-year span between the publications of these documents, but some adaptations and interpretations still need to be made to the Annex 30 approach for a good approach to a TCS system of similar nature as the one studied in this report. Review of the latest research on the kinetics and reaction path of the SrCl2-NH3 reaction pair revealed that the 100-year-old single-line-and-path reaction expression is an oversimplification of the actual chemistry. The reaction path seems to be dependent on the kinetics of the reaction, and varies with heating rate, temperature, and pressure. Various literature was found and compared, which show that the reaction enthalpies and entropies are not settled science. This demonstrates the necessity for further research into the SrCl2-NH3 reaction pair before application-scale product design and commercialization can take place. A comprehensive equipment and system review was conducted, whereby multiple issues were found and addressed, that if gone unnoticed, would have caused difficult setbacks for the project.  Consequently, the previous purchased ammonia flow meters and ammonia compressor, were exchanged for new and better suiting equipment. The original ammonia flow meters were undersized due to miscalculations of converting flow units of NLPH (Normal Liters Per Hour) to the project units of g/s, while wrongly using the density of compressed ammonia to convert to g/s, instead of it at the defined normal conditions. Furthermore, these flow meters were of the wrong type, as they had no digital output for data acquisition. The original compressor was also severely undersized, only capable of evacuating 7-14% of the expected maximum desorption flow. This was due to a similar miscalculation during conversion of NLMP (Normal Liters Per Minute) to g/s, as well as an unrequested compressor stroke reduction. New solutions and additional equipment were then required to accommodate the operational limitations discovered in the final chosen equipment and system configuration. These include limiting the compressor inlet pressure to a maximum of 1.1 bar(a); avoiding risk of NH3 condensation at them inlets of the new mass flow meters and compressor; and maintaining the flow meter and compressor inlet temperatures below 40 °C. The pressure limitations required considerable design adaptations. Firstly, an ammonia by-pass is introduced to keep feeding ammonia into the compressor during low desorption flows. The inlet pressure limitation necessitated active pressure management in the form of pressure reduction valves, which were thus introduced. Secondly, the condensation regulation and temperature management required a new approach, as the cooling and condensation temperatures in the original design were too low, causing risks of far too low temperature and pressure in the desorption path, as well as counter-acting simultaneous heating and cooling between the condenser and the storage tank heating sleeve. As a solution, a shunt pump is proposed, where constant cooling water temperature provides condensation on a tight temperature range using an infinite cold wall approach. Along with reviewing the equipment and the system design, new procedures concerning investigating and confirming homogeneous heat transfer properties of the reactors are proposed. Furthermore, improvements are suggested concerning the commissioning of the experimental rig, that include equipment testing with N2-gas and stepwise changes in temperature in sequential cycles to gain a good understanding of the likely behaviors of the system before it is run at the extremes of the operating range. In conclusion, a new and improved process flow diagram, showing all these adaptations, additions, and changes from the original diagram is presented herein as the final key contribution to the overarching NHS-project. This is complemented with an instruction manual, to allow the next researchers a smooth continuation, in terms of the system build, and later commissioning and operation. Finally, some suitable next steps in the project are suggested. These include a conceptualization of descriptive functions for the performance and behavior of the specific system and reactors. These functions are proposed with temperature and pressure as independent variables, as these are two main variables influencing the kinetics of the reaction in the given system. As no experimental data exists yet, the form of the proposed functions is generic. Furthermore, a suggestion is made for a future adaptation for achieving the phase change from NH3(g) to NH3(l) (which is the storage form of ammonia in the system) by deep cooling at the desorption pressure, resulting in only a liquid pump being required to raise the pressure of the NH3(l) in the storage tank. / Termokemisk energilagring (TCS) är en teknik inom termisk energilagring (TES) som används för att lagra termisk energi för senare bruk. TCS kan tillhandahålla värme och kyla från periodvis tillgänglig termisk energi, ofta lågtemperatur spillvärme. Systemet lagrar energin som kemisk energi genom att använda reversibla kemiska reaktioner och massaseparation av reaktions-produkterna. TCS har potential att minska utsläppet av växthusgaser, öka effektiviteten av system i vår infrastruktur, minska energikostnader i samhället och därmed bidra till hållbar utveckling. Detta exjobbsprojekt är en del av ett gemensamt TCS-forskningsprojekt som heter Neutrons for Heat Storage (NHS), där tre forskningsinstitut deltar. Projektet är finansierat av Nordforsk och Kungliga Tekniska Högskolan. KTH:s mål med NHS-projektet är att projektera, bygga, samt driva ett TCSsystem i bänkskala med strontiumklorid (SrCl2) och ammoniak (NH3) som ett fast-gasreaktionssystem för lågtemperaturvärmelagring (40-80 ℃). Här används absorption av NH3 till SrCl2⋅NH3 (monoammin) för att bilda SrCl2⋅8NH3 (oktaammin) för värmeurladdning och desorption (av NH3 från SrCl2⋅NH3 till SrCl2⋅NH3) för värmelagring. Innan detta exjobbsprojekt började hade detta TCS-system, samt systemets reaktor+värmeväxlare (R-HEX) enheter varit numeriskt projekterad vid KTH, och R-HEX-enheterna hade redan tillverkats. Detta system byggs nu på laboratoriet för Avdelningen för tillämpad termodynamik och kylning vid Institutionen för Energiteknik, KTH. Det initiala systemet består av en gemensam lagringstank, expansionsventil, ammoniakmätare, och en R-HEX (systemets absorptionssida) och en R-HEX, ammoniakmätare, gaskylare, kompressor, en kondensor, och en gemensamma lagringstanken (desorptionssidan), for att rymma absorption, desorption (samtidigt) och NH3-lagring. Exjobbsprojektet var ursprungligen planerat att inkludera driftsättning, drift och experimentdatainsamling samt utvärdering av systemet. På grund av olika förseningar och brister som upptäcktes i projektet, omdefinierades projektets mål och består nu av att granska systemet och, samt att föreslå nödvändiga designanpassningar av det ursprungligen konstruerade systemet och dess komponenter. Projektet var delvis ett gemensamt arbete, där Harish Seetharaman utförde olika uppgifter i det övergripande NHS projektet som en del av sitt eget exjobbssprojekt. För olika uppgifter och resultat kommer det därför att vara nödvändigt att hänvisa till Harishs rapport. Litteraturstudié av forskningen kring SrCl2-NH3 system genomfördes, med betoning på prestandautvärdering, kinetik och reaktionsvägar. Prestandautvärdering av TES system diskuteras angående TCS-nyckelindikatorer, med 2018 års IEA:s Annex 30 som riktlinje och IRENA:s E17 Teknologi-sammandrag från 2013 som en referens. Många framsteg och förbättringar har gjorts under femårsperioden mellan dessa publikationer, men vissa anpassningar och tolkningar måste fortfarande härledas till metoderna i Annex 30 för att få ett bra förhållningssätt till ett TCS-system av liknande karaktär som det som studeras i detta projekt. Granskning av den senaste forskningen avseende reaktionskinetik och reaktionsvägar för SrCl2-NH3 reaktionsparet visade att det hundraåriga enkellinje-och-reaktionsväg-formuleringen är en förenkling av den faktiska kemin. Reaktionsvägen verkar beroende av reaktionens kinetik och varierar med uppvärmnings-takten, temperaturen och även trycket. Olika litteratur jämfördes som visar att reaktionsentalpierna och entropierna inte är fastställd vetenskap. Detta visar behovet av ytterligare forskning avseende SrCl2-NH3 innan produktdesign och kommersialisering i applikations-skala kan utföras. En omfattande granskning av systemet och dess komponenter genomfördes, där flera problem hittades och åtgärdades. Om dessa problem hade gått obemärkt förbi skulle det ha orsakat svåra bakslag för projektet. Följaktligen byttes de tidigare köpta ammoniakflödesmätarna ut till nya och en ammoniakkompressor byttes ut mot en ny, för tillämpningen bättre anpassad. De ursprungliga ammoniak-flödesmätarna var underdimensionerade pga. felberäkningar i omvandling av flödesenheter för NLPH (normal liter per timme) till projektenheterna g/s. Samtidigt var densiteten av komprimerad ammoniak felaktigt använt för omvandling till g/s, istället för densiteten vid de definierade normala förhållandena; 1 bar (a) och 20 ° C. Dessutom var dessa flödesmätare av fel typ, eftersom de inte hade någon digital utgång för datainsamling. Den ursprungliga kompressorn var också kraftigt underdimensionerad, endast kapabel att evakuera 7-14% av det förväntade maximala desorptionsflödet. Detta berodde på en liknande felberäkning vid konvertering av NLPM (normal liter per minute) till g/s, samt en oönskad kompressorslagsminskning. Nya lösningar och ytterligare utrustning krävdes för att tillgodose de operativa begränsningar som upptäcktes i den slutgiltigt valda utrustningen och systemutformningen. Dessa inkluderar: begränsa kompressorns inloppstryck till maximalt 1,1 bar(a); undvika risk för NH3 kondens i de nya massflödesmätarna och kompressorn; samt bibehålla flödesmätarens och kompressorns inloppstemperaturer under 40 °C. Tryckbegränsningarna krävde omfattande projekteringsanpassningar. För det första införs en ammoniak-by-pass för att fortsätta mata ammoniak till kompressorn under låga desorptionsflöden. Inloppstrycksbegränsningen nödvändiggjorde aktiv tryckhantering i form av tryckreduceringsventiler. För det andra krävde kondensregleringen och temperaturhanteringen en ny strategi, eftersom kyl- och kondenseringstemperaturerna i den ursprungliga utformningen var för låga. Detta orsakade risker för alldeles för låg temperatur och tryck på desorptionssidan, samt samtidigt motverkande uppvärmning och kylning av kondensorn och förvaringstankens värmehylsa. Som en lösning föreslås en shunt där konstant kylvattentemperatur ger kondens i ett tätt temperaturintervall med en oändlig kallväggsinriktning. Tillsammans med granskning av utrustningen och systemutformningen föreslås nya tillvägagångssätt för undersökning och bekräftelse av reaktorers förmodade homogena värmeöverförings-egenskaper. Dessutom föreslås förbättringar av idrifttagningen av den experimentella riggen, som inkluderar utrustningstestning med N2-gas och stegvisa temperaturförändringar i sekventiella körningar för att få en god förståelse för systemets troliga beteenden innan det körs i ytterligheterna av systemts arbetsområde. Sammanfattningsvis presenteras ett nytt och förbättrat processflödesdiagram, som visar alla utförda anpassningar, tillägg och ändringar från det ursprungliga diagrammet, som är avhandlingsprojektets huvudbidrag till det övergripande NHS-projektet. Detta kompletteras med en bruksanvisning för att smidigt fasa in kommande forskare avseende systemets konstruktion, driftsättning, och drift. Slutligen föreslås några lämpliga kommande steg i projektet. Dessa inkluderar en konceptualisering av beskrivande funktioner för prestanda och beteende av det specifika systemet och reaktorer. Dessa funktioner föreslås med temperatur och tryck som oberoende variabler, eftersom dessa är två huvudvariabler som påverkar reaktionens kinetik. Eftersom inga experimentella data ännu finns, är formen för de föreslagna funktionerna generisk. Vidare ges förslag om framtida anpassning för att uppnå fasändringen från NH3(g) till NH3(v) (som är lagringsformen för NH3 i systemet) genom djup nedkylning vid desorptionstrycket, vilket resulterar i att endast en vätskepump krävs för att höja trycket för NH3(v) i lagringstanken.

Le travail de la thèse s’articule sur le développement d’un nouveau type de capteurs de gaz à base des matériaux semi-conducteurs III-Nitrure (Les nitrures de gallium). Ces matériaux présentent de nombreux avantages qui pourraient être utilisées pour concevoir des capteurs NOx sensibles et sélectifs pour le contrôle des pollutions émises par la ligne d’échappement Diesel. Afin de limiter et déduire les gaz polluants émis par les moteurs à explosion en générale et les moteurs Diesel en particuliers (NO, NO2, NH3, CO, …), différentes normes européennes ont été établies. Pour respecter ces normes, plusieurs modifications sur les moteurs et les lignes d’échappement des véhicules ont été effectuées (filtres à particules, catalyseurs, capteurs NOx, …). Les capteurs NOx utilisés actuellement sont à base d’électrolyte solide. Ils sont basés dans leur fonctionnement sur la mesure de la concentration d’oxygène présente dans le gaz d’échappement qui permet de son tour l’estimation de la concentration totale des gaz NOx (mesure indirecte). Ces capteurs ne détectent pas le NH3 à la sortie de la ligne d’échappement, et ne donnent pas une information précise sur le rapport entre NO et NO2 (manque de sélectivité) qui est un facteur important pour le bon fonctionnement de catalyseur sélectif SCR (amélioration de rendement) ; d’où la nécessité d’un capteur de gaz plus performant et en particulier sélectif afin d’améliorer les systèmes de contrôle, de post-traitement et de diagnostic. Notre approche consiste à utiliser un transistor HEMT (High Electron Mobility Transistor) à gaz bidimensionnel d’électrons à base de nitrure de Gallium avec l’association d’une couche fonctionnelle à la place de la grille. L’interaction des molécules de gaz avec cette couche fonctionnelle donne une signature (variation de signal de sortie) spécifique pour chaque type de gaz qui aide à l’amélioration de la sélectivité. Le projet contient deux parties : l’optimisation de la structure choisie et l’optimisation de la couche fonctionnelle afin d’obtenir une détection sélective entre les différents gaz polluants. Cette technologie est intéressante pour développer des capteurs de gaz grâce aux possibilités de détecter des faibles variations de tensions et aux possibilités de fonctionnement dans des environnements sévères. La thèse de doctorat s’inscrit dans le cadre de l’OpenLab materials and processes en collaboration entre le laboratoire Georgia-Tech lorraine et l’entreprise Peugeot-Citroën PSA / The work of the thesis focuses on the development of a new type of gas sensors based III-Nitride semiconductor materials (gallium nitrides). These materials have many advantages that could be used to develop sensitive and selective NOx sensors for the control of pollution emitted by diesel exhaust line. To limit the polluting gases emitted by internal combustion engines in general and diesel in particular (NO, NO2, NH3, CO, ...), different European standards have been established. To meet these standards, anti-pollution systems (consisting of particle filters, catalysts, NOx sensors, ... etc) are used. NOx sensors currently used in automobiles are based on a solid electrolyte. Their operation is based on the measurement of the oxygen concentration. This enables an estimate of the total concentration of NOx gas (indirect measurement) after filtering NOx from O2 and decomposing NOx into O2. These sensors do not detect NH3 at the outlet of the exhaust line, and do not give accurate information on the relationship between NO and NO2 (lack of selectivity) which is important factor for an optimal functioning of selective catalyst (SCR performance improvement). Hence there exists a need for a more efficient and selective in particular gas sensor to improve the control systems, post-treatment and diagnosis. Our approach is to use a HEMT (High Electron Mobility Transistor) transistor based on gallium nitride with a combination of a functional layer instead of the gate. The interaction of the gas molecules with the functional layer gives a signature (output signal variation) specific for each type of gas that helps to improve the selectivity. The project contains two parts: the optimization of the chosen structure and the optimization of the functional layer in order to achieve selective detection between various gaseous pollutants. This technology is interesting for development of gas sensors through the possibility of detection low voltage variations and the possibility of operating in harsh environments. The thesis is part of OpenLab "Materials and Processes" in a collaboration between Georgia Tech-CNRS laboratory and the PSA Peugeot-Citroen Group

Comparative studies over micro-/mesoporous Cu-containing zeolites ZSM-5 prepared by top-down treatment involving NaOH, TPAOH or mixture of NaOH/TPAOH (tetrapropylammonium hydroxide) were conducted. The results of the catalytic data revealed the highest activity of the Cu-ZSM-5 catalyst both in the absence and presence of water vapor. The physico-chemical characterization (diffuse reflectance UV-Vis (DR UV-Vis), Fourier transform infrared (FT-IR) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, temperature-programmed desorption of NOx (TPD-NOx), and microkinetic modeling) results indicated that the microporous structure of ZSM-5 effectively stabilized isolated Cu ion monomers. Besides the attempts targeted to the modification of the textural properties of the parent ZSM-5, in the next approach, we studied the effect of the co-presence of sodium and copper cations in the microporous H-ZSM-5. The presence of co-cation promoted the evolution of [Cu–O–Cu]2+ dimers that bind NOx strongly with the desorption energy barrier of least 80 kJ mol−1. Water presence in the gas phase significantly decreases the rate of ammonia oxidation, while the reaction rates and activation energies of NH3-SCR remain unaffected.

Nanosized SSZ-13 was synthesized hydrothermally by applying N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as a structure-directing agent. In the next step, the quantity of TMAdaOH in the initial synthesis mixture of SSZ-13 was reduced by half. Furthermore, we varied the sodium hydroxide concentration. After ion-exchange with copper ions (Cu2+ and Cu+), the Cu-SSZ-13 catalysts were characterized to explore their framework composition (XRD, solid-state NMR, ICP-OES), texture (N2-sorption, SEM) and acid/redox properties (FT-IR, TPR-H2, DR UV-Vis, EPR). Finally, the materials were tested in the selective catalytic reduction of NOx with ammonia (NH3-SCR). The main difference between the Cu-SSZ-13 catalysts was the number of Cu2+ in the double six-membered ring (6MRs). Such copper species contribute to a high NH3-SCR activity. Nevertheless, all materials show comparable activity in NH3-SCR up to 350 °C. Above 350 °C, NO conversion decreased for Cu-SSZ-13(2–4) due to side reaction of NH3 oxidation.

O N é um nutriente empregado em grandes quantidades nos sistemas de produção agrícola e o mais limitante para a produção de gramíneas. A ureia é o fertilizante nitrogenado (N-fertilizante) mais usado no mundo e o principal foco da indústria mundial de fertilizantes tecnologicamente aperfeiçoados, sendo altamente suscetível à perdas por volatilização de amônia (NH3), quando aplicada sobre superfície do solo. Com intuito de minimizar o impacto ambiental e aumentar a eficiência de N, o uso de inibidores de urease é uma das tecnologias mais promissoras e menos onerosas. Adicionalmente, inibidores de urease inorgânicos constituídos por elementos essenciais às plantas, como ácido bórico (H3BO3) e sulfato de cobre (CuSO4), podem suplementar nutricionalmente os sistemas agrícolas de produção. Neste contexto, foram desenvolvidos dois experimentos, em condições controladas de laboratório e casa de vegetação, com os seguintes objetivos: i) quantificar as perdas por volatilização de NH3 a partir da aplicação superficial da ureia tratada com doses variadas de H3BO3 e CuSO4, em câmara fechada; ii) avaliar a eficiência de uso de N e B em dois estádios vegetativos do milho a partir da aplicação em superfície da 15N-ureia tratada com H3BO3 e CuSO4, em condições controladas de casa de vegetação. No experimento de laboratório, não houve interação entre as doses de B e Cu ou qualquer efeito do Cu sobre as perdas de NH3 por volatilização. O aumento de H3BO3 no tratamento da U atrasou as perdas diárias de NH3 e reduziu (P<0,001) as perdas cumulativas de volatilização de NH3. As doses de B apresentaram ajuste quadrático e, com base na análise de regressão, a dose estimada de máxima eficiência é atingida com 0,88% B no recobrimento da U. Em condições de casa de vegetação, os inibidores de urease atrasaram e reduziram as perdas de NH3 por volatilização. Ao longo de 15 dias após a fertilização, o tratamento com H3BO3 promoveu reduções na volatilização de NH3 que variaram de 6 a 17% em relação à ureia não tratada, ocorrendo diferenciação entre doses de B. Os tratamentos com maiores doses de B não diferiram do tratamento com N-(n-butil) tiofosfórico triamida (NBPT) em produção de biomassa de milho. A altura de plantas, diâmetro de colmo e índice de área foliar não apresentaram diferenças entre N-fertilizantes. A morfologia do sistema radicular do milho foi afetada pelo uso de inibidores no estádio V8. O aumento de H3BO3 no revestimento da ureia aumentou em média 10% a eficiência de uso do N-fertilizante (EUN-F), em relação à ureia não tratada. Em VT, não houve diferença para EUN-F entre os tratamentos NBPT e maior dose de H3BO3 (0,88% B). O tratamento da ureia com H3BO3 aumentou proporcionalmente o acúmulo de B na planta. A adição de CuSO4 não afetou a volatilização de NH3 e a EUN-F. O recobrimento da ureia com H3BO3 foi uma estratégia eficiente em reduzir as perdas de N, aumentar a EUN-F e fornecer B às plantas. / N is a nutrient used in large quantities in agricultural production systems and it is the most limiting element for production of grasses. Urea is the most widely used nitrogen fertilizer (N fertilizer) in the world and the main focus of the worldwide industry of fertilizers technologically improved, being highly susceptible to losses by volatilization of ammonia (NH3) when applied on soil surface. In order to minimize environmental impact and increase N efficiency, the use of urease inhibitors is one of the most promising and least expensive technologies. In addition, inorganic urease composed for essential elements for plants, such as boric acid (H3BO3) and copper sulfate (CuSO4), can nutritionally supplement agricultural production systems. In this context, two experiments were carried out under controlled conditions (laboratory and greenhouse) with the following objectives: i) laboratory: to quantify NH3 volatilization losses from the surface application of urea treated with different rates of H3BO3 and CuSO4, using closed chamber; (ii) greenhouse: to evaluate the N and B use efficiency from surface application of 15N urea treated with H3BO3 and CuSO4 in two vegetative stages of maize. In the laboratory experiment, there was no interaction between B and Cu rates or any Cu effect on NH3 losses by volatilization. The increase of H3BO3 in the treatment of urea delayed the daily losses of NH3 and reduced (P<0.001) the cumulative volatilization losses of NH3. The rates of B showed a quadratic adjustment and, based on the regression analysis, the estimated rate of maximum efficiency was 0.88% B. Under greenhouse conditions, urease inhibitors delayed and decresed the losses of NH3 by volatilization. Over 15 days after fertilization, treatment with H3BO3 promoted reductions in NH3 volatilization ranging from 6 to 17% compared to untreated urea, and occur differentiation between B rates. The treatments with higher rates of B did not differ from the treatment with N-(n-butyl) thiophosphoric triamide (NBPT) in maize biomass production. The plant height, stem diameter and leaf area index did not show differences between N fertilizers. The morphology of the maize root system was affected by the use of urease inhibitors only in stage V8. The increase of H3BO3 in the urea coating increased on average 10% the efficiency of use of N fertilizer (NUE-F) in relation to untreated urea. In VT growth stage, there was no difference for NUE-F between treatments NBPT and higher rate of H3BO3 (0.88% B). Treatment of U with H3BO3 increased proportionally the accumulation of B in the plant. The addition of CuSO4 did not affect volatilization of NH3 and NUE-F. Urea coating with H3BO3 was an efficient strategy to reduce N losses, to increase the NUE-F and to supply B for plants.

O N é um nutriente empregado em grandes quantidades nos sistemas de produção agrícola e o mais limitante para a produção de gramíneas. A ureia é o fertilizante nitrogenado (N-fertilizante) mais usado no mundo e o principal foco da indústria mundial de fertilizantes tecnologicamente aperfeiçoados, sendo altamente suscetível à perdas por volatilização de amônia (NH3), quando aplicada sobre superfície do solo. Com intuito de minimizar o impacto ambiental e aumentar a eficiência de N, o uso de inibidores de urease é uma das tecnologias mais promissoras e menos onerosas. Adicionalmente, inibidores de urease inorgânicos constituídos por elementos essenciais às plantas, como ácido bórico (H3BO3) e sulfato de cobre (CuSO4), podem suplementar nutricionalmente os sistemas agrícolas de produção. Neste contexto, foram desenvolvidos dois experimentos, em condições controladas de laboratório e casa de vegetação, com os seguintes objetivos: i) quantificar as perdas por volatilização de NH3 a partir da aplicação superficial da ureia tratada com doses variadas de H3BO3 e CuSO4, em câmara fechada; ii) avaliar a eficiência de uso de N e B em dois estádios vegetativos do milho a partir da aplicação em superfície da 15N-ureia tratada com H3BO3 e CuSO4, em condições controladas de casa de vegetação. No experimento de laboratório, não houve interação entre as doses de B e Cu ou qualquer efeito do Cu sobre as perdas de NH3 por volatilização. O aumento de H3BO3 no tratamento da U atrasou as perdas diárias de NH3 e reduziu (P<0,001) as perdas cumulativas de volatilização de NH3. As doses de B apresentaram ajuste quadrático e, com base na análise de regressão, a dose estimada de máxima eficiência é atingida com 0,88% B no recobrimento da U. Em condições de casa de vegetação, os inibidores de urease atrasaram e reduziram as perdas de NH3 por volatilização. Ao longo de 15 dias após a fertilização, o tratamento com H3BO3 promoveu reduções na volatilização de NH3 que variaram de 6 a 17% em relação à ureia não tratada, ocorrendo diferenciação entre doses de B. Os tratamentos com maiores doses de B não diferiram do tratamento com N-(n-butil) tiofosfórico triamida (NBPT) em produção de biomassa de milho. A altura de plantas, diâmetro de colmo e índice de área foliar não apresentaram diferenças entre N-fertilizantes. A morfologia do sistema radicular do milho foi afetada pelo uso de inibidores no estádio V8. O aumento de H3BO3 no revestimento da ureia aumentou em média 10% a eficiência de uso do N-fertilizante (EUN-F), em relação à ureia não tratada. Em VT, não houve diferença para EUN-F entre os tratamentos NBPT e maior dose de H3BO3 (0,88% B). O tratamento da ureia com H3BO3 aumentou proporcionalmente o acúmulo de B na planta. A adição de CuSO4 não afetou a volatilização de NH3 e a EUN-F. O recobrimento da ureia com H3BO3 foi uma estratégia eficiente em reduzir as perdas de N, aumentar a EUN-F e fornecer B às plantas. / N is a nutrient used in large quantities in agricultural production systems and it is the most limiting element for production of grasses. Urea is the most widely used nitrogen fertilizer (N fertilizer) in the world and the main focus of the worldwide industry of fertilizers technologically improved, being highly susceptible to losses by volatilization of ammonia (NH3) when applied on soil surface. In order to minimize environmental impact and increase N efficiency, the use of urease inhibitors is one of the most promising and least expensive technologies. In addition, inorganic urease composed for essential elements for plants, such as boric acid (H3BO3) and copper sulfate (CuSO4), can nutritionally supplement agricultural production systems. In this context, two experiments were carried out under controlled conditions (laboratory and greenhouse) with the following objectives: i) laboratory: to quantify NH3 volatilization losses from the surface application of urea treated with different rates of H3BO3 and CuSO4, using closed chamber; (ii) greenhouse: to evaluate the N and B use efficiency from surface application of 15N urea treated with H3BO3 and CuSO4 in two vegetative stages of maize. In the laboratory experiment, there was no interaction between B and Cu rates or any Cu effect on NH3 losses by volatilization. The increase of H3BO3 in the treatment of urea delayed the daily losses of NH3 and reduced (P<0.001) the cumulative volatilization losses of NH3. The rates of B showed a quadratic adjustment and, based on the regression analysis, the estimated rate of maximum efficiency was 0.88% B. Under greenhouse conditions, urease inhibitors delayed and decresed the losses of NH3 by volatilization. Over 15 days after fertilization, treatment with H3BO3 promoted reductions in NH3 volatilization ranging from 6 to 17% compared to untreated urea, and occur differentiation between B rates. The treatments with higher rates of B did not differ from the treatment with N-(n-butyl) thiophosphoric triamide (NBPT) in maize biomass production. The plant height, stem diameter and leaf area index did not show differences between N fertilizers. The morphology of the maize root system was affected by the use of urease inhibitors only in stage V8. The increase of H3BO3 in the urea coating increased on average 10% the efficiency of use of N fertilizer (NUE-F) in relation to untreated urea. In VT growth stage, there was no difference for NUE-F between treatments NBPT and higher rate of H3BO3 (0.88% B). Treatment of U with H3BO3 increased proportionally the accumulation of B in the plant. The addition of CuSO4 did not affect volatilization of NH3 and NUE-F. Urea coating with H3BO3 was an efficient strategy to reduce N losses, to increase the NUE-F and to supply B for plants.

This thesis concerns catalytic combustion for gas turbineapplication using a low heating-value (LHV) gas, derived fromgasified waste. The main research in catalytic combustionfocuses on methane as fuel, but an increasing interest isdirected towards catalytic combustion of LHV fuels. This thesisshows that it is possible to catalytically combust a LHV gasand to oxidize fuel-bound nitrogen (NH3) directly into N2without forming NOX. The first part of the thesis gives abackground to the system. It defines waste, shortly describesgasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns thedevelopment and testing of potential catalysts for catalyticcombustion of LHV gases. The objective of this work was toinvestigate the possibility to use a stable metal oxide insteadof noble metals as ignition catalyst and at the same timereduce the formation of NOX. In paper II pilot-scale tests werecarried out to prove the potential of catalytic combustionusing real gasified waste and to compare with the resultsobtained in laboratory scale using a synthetic gas simulatinggasified waste. In paper III, selective catalytic oxidation fordecreasing the NOX formation from fuel-bound nitrogen wasexamined using two different approaches: fuel-lean andfuel-rich conditions. Finally, the last part of the thesis deals with deactivationof catalysts. The various deactivation processes which mayaffect high-temperature catalytic combustion are reviewed inpaper IV. In paper V the poisoning effect of low amounts ofsulfur was studied; various metal oxides as well as supportedpalladium and platinum catalysts were used as catalysts forcombustion of a synthetic gas. In conclusion, with the results obtained in this thesis itwould be possible to compose a working catalytic system for gasturbine application using a LHV gas. <b>Keywords:</b>Catalytic combustion; Gasified waste; LHVfuel; RDF; Biomass; Selective catalytic oxidation; NH3; NOX;Palladium; Platinum; Hexaaluminate; Garnet; Spinel;Deactivation; Sulfur; Poisoning

<p>This thesis concerns catalytic combustion for gas turbineapplication using a low heating-value (LHV) gas, derived fromgasified waste. The main research in catalytic combustionfocuses on methane as fuel, but an increasing interest isdirected towards catalytic combustion of LHV fuels. This thesisshows that it is possible to catalytically combust a LHV gasand to oxidize fuel-bound nitrogen (NH3) directly into N2without forming NOX. The first part of the thesis gives abackground to the system. It defines waste, shortly describesgasification and more thoroughly catalytic combustion.</p><p>The second part of the present thesis, paper I, concerns thedevelopment and testing of potential catalysts for catalyticcombustion of LHV gases. The objective of this work was toinvestigate the possibility to use a stable metal oxide insteadof noble metals as ignition catalyst and at the same timereduce the formation of NOX. In paper II pilot-scale tests werecarried out to prove the potential of catalytic combustionusing real gasified waste and to compare with the resultsobtained in laboratory scale using a synthetic gas simulatinggasified waste. In paper III, selective catalytic oxidation fordecreasing the NOX formation from fuel-bound nitrogen wasexamined using two different approaches: fuel-lean andfuel-rich conditions.</p><p>Finally, the last part of the thesis deals with deactivationof catalysts. The various deactivation processes which mayaffect high-temperature catalytic combustion are reviewed inpaper IV. In paper V the poisoning effect of low amounts ofsulfur was studied; various metal oxides as well as supportedpalladium and platinum catalysts were used as catalysts forcombustion of a synthetic gas.</p><p>In conclusion, with the results obtained in this thesis itwould be possible to compose a working catalytic system for gasturbine application using a LHV gas.</p><p><b>Keywords:</b>Catalytic combustion; Gasified waste; LHVfuel; RDF; Biomass; Selective catalytic oxidation; NH3; NOX;Palladium; Platinum; Hexaaluminate; Garnet; Spinel;Deactivation; Sulfur; Poisoning</p>

The reaction mechanism for the selective catalytic reduction (SCR) of nitric oxide by ammonia on (010) V2O5 surface represented by a V2O9H8 cluster was simulated by density functional theory (DFT) calculations. The computations indicated that SCR reaction consisted of three main parts. In the first part ammonia activation on Br&oslash / nsted acidic V-OH site as NH4+ species by a nonactivated process takes place. The second part includes the interaction of NO with pre-adsorbed NH4 + species to eventually form nitrosamide (NH2NO). The rate limiting step for this part as well as for the total SCR reaction is identified as NH3NHO formation reaction. The last part consists of the decomposition of NH2NO on the cluster which takes advantage of a hydrogen transfer mechanism between the active V=O and V-OH groups. Water and ammonia adsorption and dissociation are investigated on (101) and (001) anatase surfaces both represented by totally fixed and partially relaxed Ti2O9H10 clusters. Adsorption of H2O and NH3 by H-bonding on previously H2O and NH3 dissociated systems are also considered. By use of a (001) relaxed Ti2O9H10 cluster, the role of anatase support on SCR reaction is investigated. Since NH2NO formation on Ti2O9H10 cluster requires lower activation barriers than on V2O5 surface, it is proposed that the role of titanium dioxide on SCR reaction could be forming NH2NO. The role of vanadium oxide is crucial in terms of dissociating this product into H2O and N2. Finally, NH3 adsorption is studied on a V2TiO14H14 cluster which represents a model for vanadia/titania surface.